G
H. Li et al.
Paper
Synthesis
GC-MS (EI): m/z = 280.2, 223.2, 144.2, 134.2, 121.1, 104.1, 91.1, 78.0,
HRMS (EI): m/z [M + H]+ calcd for C17H18O: 238.1358; found:
65.0, 51.0.
238.1352.
HRMS (EI): m/z [M + H]+ calcd for C19H20O2: 280.1463; found:
280.1458.
(3R,5R)-3-Methyl-5-(naphthalen-2-yl)cyclohexan-1-one (3n; Table
2, Entry 14)8
28
Yield: 21.6 mg (45%); white solid; mp 82.4–84.7 °C; 74% ee; [α]D
–9.4 (c 0.70, CH2Cl2) {reported value of (3R,5R)-3n:8 80% ee; [α]D
=
=
(3R,5R)-3-(4-Chlorophenyl)-5-phenylcyclohexan-1-one (3k; Table
2, Entry 11)
–5.4 (c 0.70, CH2Cl2)}; HPLC (Chiralpak IC; 4.6 mm × 250 mm; hex-
ane/i-PrOH, 95:5; 0.7 mL/min; 214 nm): tR = 18.73 (major), 19.61 (mi-
nor) min.
28
Yield: 24.3 mg (43%); yellow solid; mp 59.0–59.8 °C; 72% ee; [α]D
=
21.2 (c 0.75, CH2Cl2); HPLC (Chiralpak IC; 4.6 mm × 250 mm; hex-
ane/i-PrOH, 80:20; 0.7 mL/min; 214 nm): tR = 9.11 (major), 10.65 (mi-
nor) min.
IR (film): 3054.59, 2953.79, 2923.90, 1703.92, 1204.92, 1217.52,
950.28, 900.69, 859.73, 814.31, 741.23 cm–1
.
IR (film): 2896.67, 2871.23, 1704.32, 1491.41, 1242.67, 1090.26,
838.55, 818.52, 698.92 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.98–7.88 (m, 1 H), 7.81–7.79 (m, 3 H),
7.62 (s, 1 H), 7.54–7.43 (m, 1 H), 7.37 (dd, J = 8.8, 2.0 Hz, 1 H), 3.59–
3.52 (m, 1 H), 2.78–2.56 (m, 3 H), 2.31–2.24 (m, 1 H), 2.22–2.15 (m,
2 H), 1.97–1.91 (m,1 H), 1.05 (d, J = 6.8 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 211.59, 141.72, 128.51, 128.25,
127.73, 127.67, 127.52, 126.17, 125.71, 125.63, 125.13, 48.58, 46.98,
39.65, 39.23, 29.21, 20.38.
1H NMR (400 MHz, CDCl3): δ = 7.33–6.83 (m, 9 H), 3.33–3.28 (m, 2 H),
2.79–2.70 (m, 4 H), 2.33–2.29 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 210.94, 143.57, 142.24, 132.32,
128.72, 128.67, 128.39, 126.96, 126.66, 46.54, 46.39, 39.36, 38.80,
38.83.
MS (EI): m/z = 284, 266, 249, 227, 206, 152, 138, 133, 118, 104, 91, 77.
HRMS (EI): m/z [M + H]+ calcd for C18H17OCl: 284.0968; found:
GC-MS (EI): m/z = 238.1, 181.1, 154.1, 141.1, 128.1, 115.1, 83.0, 56.0.
HRMS (ESI): m/z [M + NH4]+ calcd for C17H22NO: 256.1696; found:
256.1698.
284.0962.
(3R,5R)-3-Methyl-5-phenylcyclohexan-1-one (3l; Table 2, Entry
(3R,5R)-3-(4-Methoxyphenyl)-5-methylcyclohexan-1-one (3o; Ta-
12)8
ble 2, Entry 15)8
27
Yield: 17.1 mg (46%); colorless oil; 81% ee; [α]D = –20.4 (c
28
Yield: 18.6 mg (43%); colorless oil; 64% ee; [α]D = –8.7 (c 0.69,
0.50,CH2Cl2) {reported value of (3R,5R)-3l:8 81% ee; [α]D = –22.3 (c
0.50, CH2Cl2)}; HPLC (Chiralpak IC; 4.6 mm × 250 mm; hexane/i-PrOH,
98:2; 0.5 mL/min; 210 nm): tR = 28.25 (major), 32.17 (minor) min.
CH2Cl2) {reported value of (3R,5R)-3o:8 86% ee; [α]D = –20.0 (c 0.30,
CH2Cl2)}; HPLC (Chiralpak IC; 4.6 mm × 250 mm; hexane/i-PrOH,
90:10; 0.5 mL/min; 280 nm): tR = 23.68 (major), 26.03 (minor) min.
IR (film): 2957.51, 2923.94, 1710.74, 1453.22, 1261.27, 1239.42,
IR (film): 2954.81, 2922.48, 1707.25, 1611.17, 1511.89, 1458.52,
1074.89, 1026.17, 799.82, 757.21, 701.24 cm–1
.
1246.93, 1179.68, 1033.26, 872.84, 830.64 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.32 (t, J = 6.8 Hz, 2 H), 7.24–7.20 (m,
3 H), 3.42–3.35 (m, 1 H), 2.65–2.53 (m, 3 H), 2.31–2.24 (m, 1 H), 2.18
(dd, J = 14.0, 6.4 Hz, 1 H), 2.11–2.04 (m, 1 H), 1.90–1.84 (m, 1 H), 1.04
(d, J = 7.2 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 211.60, 144.30, 128.56, 126.91,
126.47, 48.42, 47.16, 39.51, 39.30, 29.24, 20.26.
1H NMR (400 MHz, CDCl3): δ = 7.15–7.11 (m, 2 H), 6.89–6.84 (m, 2 H),
3.79 (s, 3 H), 3.36–3.31 (m, 1 H), 2.58–2.52 (m, 3 H), 2.28–2.22 (m,
1 H), 2.18–2.13 (m, 1 H), 2.07–2.00 (m, 1 H), 1.87–1.81 (m, 1 H), 1.03
(d, J = 6.8 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 211.84, 158.09, 136.45, 127.88,
113.89, 55.26, 48.48, 47.45, 39.50, 38.77, 29.22, 20.31.
GC-MS (EI): m/z = 188.1, 173.1, 131.1, 118.1, 104.1, 91.1, 78.1, 56.1,
51.0.
HRMS (ESI): m/z [M + H]+ calcd for C13H17O: 189.1274; found:
189.1274.
GC-MS (EI): m/z = 218.1, 161.1, 146.1, 134.2, 119.1, 103.1, 91.1, 77.0,
56.1.
HRMS (EI): m/z [M + H]+ calcd for C14H18O2: 218.1307; found:
218.1302.
(3R,5R)-3-Methyl-5-(naphthalen-1-yl)cyclohexan-1-one (3m; Ta-
(3R,5R)-3-Isopropyl-5-phenylcyclohexan-1-one (3p; Table 2, Entry
16)
ble 2, Entry 13)8
28
Yield: 20.4 mg (43%); colorless oil; 76% ee; [α]D = –78.1 (c 0.44,
28
Yield: 18.4 mg (43%); colorless oil; 85% ee; [α]D = –27.7 (c 0.80,
CH2Cl2) {reported value of (3R,5R)-3m:8 87% ee; [α]D = –19.7 (c 1.00,
CH2Cl2)}; HPLC (Chiralpak IC; 4.6 mm × 250 mm; hexane/i-PrOH,
95:5; 0.7 mL/min; 214 nm): tR = 16.91 (major), 18.28 (minor) min.
CH2Cl2); HPLC (Chiralpak IC; 4.6 mm × 250 mm; hexane/i-PrOH, 98:2;
0.5 mL/min; 210 nm): tR = 24.48 (major), 29.09 (minor) min.
IR (film): 2958.41, 2874.54, 1707.71, 1451.30, 1231.21, 759.13,
IR (film): 3048.84, 2953.19, 2924.78, 1704.80, 1273.75, 1237.58,
699.24 cm–1
.
774.16, 733.22 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.34–7.30 (m, 2 H), 7.24–7.20 (m, 3 H),
3.43–3.37 (m, 1 H), 2.71–2.58 (m, 2 H), 2.48 (dd, J = 14.8, 4.8 Hz, 1 H),
2.36–2.30 (m, 1 H), 2.06–1.98 (m, 2 H), 1.73–1.64 (m, 1 H), 1.58–1.50
(m, 1 H), 0.89 (t, J = 6.0 Hz, 6 H).
13C NMR (101 MHz, CDCl3): δ = 212.28, 144.34, 128.55, 126.98,
126.41, 46.51, 44.63, 40.11, 39.38, 35.28, 30.49, 19.96, 19.92.
1H NMR (400 MHz, CDCl3): δ = 8.07 (d, J = 8.4 Hz, 1 H), 7.89 (dd, J = 8.0,
1.6 Hz, 1 H), 7.76 (d, J = 8.4 Hz, 1 H), 7.57–7.41 (m, 3 H), 7.35–7.29 (m,
1 H), 4.33–4.22 (m, 1 H), 2.77 (d, J = 6.8 Hz, 1 H), 2.65–2.59 (m, 1 H),
2.25–2.16 (m, 3 H), 2.05–1.97 (m, 1 H), 1.07 (d, J = 6.4 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 212.22, 129.12, 127.63, 127.24,
126.14, 125.58, 125.39, 125.34, 1123.48, 122.89, 48.85, 46.71, 38.50,
34.89, 29.21, 20.56.
GC-MS (EI): m/z = 216.0, 201.1, 173.2, 159.2, 146.1, 131.1, 117.2,
104.1, 91.1, 69.1, 55.0.
GC-MS (EI): m/z = 238.1, 181.1, 153.1, 128.1, 115.1, 76.0, 56.1.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H